JP5248359B2 - Method for producing resin composition - Google Patents

Description

  The present invention relates to a method for producing a hybrid type modified resin composition of epoxy and silicone.

In recent years, the market related to LEDs (light-emitting diodes) has advanced rapidly, and accordingly, the demand for high-performance and inexpensive sealing materials is also increasing.
Conventionally, an epoxy resin is often used as a material for the sealing material, but the field of use is limited because of poor performance and particularly light resistance. In particular, this tendency is remarkable for epoxy resins having an aromatic ring such as bisphenol A glycidyl ether.

  As a material for the sealing material, a silicone resin has been studied, but the silicone resin is excellent in light resistance and heat resistance, but has many problems in hardness and adhesiveness of the cured product. Moreover, since it is very expensive compared with an epoxy resin, it has a problem in practical use.

  In recent years, hybrid resins of epoxy and silicone have also been developed. However, hybrid resins of epoxy and silicone are inferior in storage stability and have a significant increase in resin viscosity during storage. However, many of them are gelled and have a problem of poor practicality.

  Other hybrid type resins include a resin composition in which an epoxy resin and a pre-condensed silicone resin are mixed (for example, see Patent Documents 1 and 2), an epoxy resin and a methoxysilane condensate are mixed, and a dealcoholization reaction. The resin composition obtained by the above (for example, see Patent Documents 3 and 4), and the resin composition obtained by mixing an epoxy resin and a tetramethoxysilane condensate and hydrolytic condensation (for example, see Patent Documents 5 and 6). ), A resin obtained by hydrolytic condensation of an alkoxysilane compound having an organic group having a cyclic ether group and an alkoxysilane compound having an organic group having an aryl group (see, for example, Patent Document 7), an epoxy resin. Modified phenoxy resin obtained by demethanol reaction with γ-glycidoxypropylmethoxysilane ( In example, see Patent Document 8.) It has been proposed.

JP 2006-241230 A JP 2006-225515 A JP 2005-179401 A JP 2003-246838 A International Publication No. 2005/081024 Pamphlet JP 2007-284621 A JP 2008-120443 A JP 2007-321130 A

However, with the rapid progress of the LED (light emitting diode) related market in recent years, it has been required to develop a resin composition that can exhibit even higher performance, particularly as a sealing material. However, there are still many points to be improved in terms of performance.
Therefore, in the present invention, there is provided a method for producing a resin composition that is excellent in fluidity, excellent in storage stability, and capable of exhibiting excellent light resistance and thermal shock resistance when cured. It was aimed.

  As a result of diligent research, the present inventors have mixed an epoxy resin and a specific alkoxysilane compound at a specific ratio, and under the condition that the condensation ratio of the intermediate can be increased, by cohydrolytic condensation. In addition, a resin composition having excellent fluidity and improved storage stability, a cured product of the resin composition capable of exhibiting excellent light resistance and thermal shock resistance, and a highly functional sealing using the resin composition The present inventors have found that a stop material can be provided, and have made the present invention.

In the invention of claim 1,
(A) a step of cohydrolyzing and condensing an epoxy resin and an alkoxysilane compound represented by the following formula (1), and the cohydrolytic condensation step is accompanied by dehydration with a condensation rate of 78% or more. There is provided a method for producing a resin composition, characterized in that an intermediate produced in a non-refluxing step is subjected to dehydration condensation.

In formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. Moreover, several R < ² > may be the same or different and shows a hydrogen atom or a C1-C8 alkyl group.

The alkoxysilane compound is
(B) n = 1 to 2, R ¹ having at least one cyclic ether group, and (C) n = 1 to 2, R ¹ being at least 1 The mixture index α of (B) and (C), which includes at least one alkoxysilane compound having one aryl group and is represented by the following formula (2), is 0.001 to 19.
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C))

  In the invention of claim 2, the epoxy resin (A) has an epoxy equivalent (WPE) of 100 to 600 g / eq and a viscosity at 25 ° C. of 1000 Pa · s or less. A method for producing the composition is provided.

  In invention of Claim 3, the said (A) epoxy resin is a glycidyl etherification product of a polyphenol compound, Comprising: The manufacturing method of the resin composition of Claim 1 or 2 which is a polyfunctional epoxy resin is provided. .

  In the invention of claim 4, the alkoxysilane compound further includes (D): at least one alkoxysilane compound in which n = 0 in the formula (1). The manufacturing method of the resin composition as described in one term is provided.

In the invention of claim 5, the mixing index β of the alkoxysilane compound represented by the following formula (3) is 0.01 to 1.4, according to any one of claims 1 to 4. A method for producing a resin composition is provided.
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
Here, in the formula (3),
β ⁿ² : Content (mol%) of the alkoxysilane compound in which n = 2 in the formula (1)
β ⁿ⁰ : Content (mol%) of the alkoxysilane compound in which n = 0 in the formula (1)
β ⁿ¹ : Content (mol%) of the alkoxysilane compound in which n = 1 in the formula (1)
And
0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1.

In invention of Claim 6, the mixing parameter | index (gamma) of the said (A) epoxy resin and the said alkoxysilane compound represented by following formula (4) is 0.02-15, Claim 1 thru | or 5 The manufacturing method of the resin composition as described in any one is provided.
Mixing index γ = (γa) / (γs) (4)
Here, in the formula (4),
γa: mass of epoxy resin (g),
γs: the mass (g) of the alkoxysilane compound in which n = 0 to 2 in the formula (1).

  In the invention of claim 7, the co-hydrolysis condensation is carried out in the presence of (E) an alkali organic metal which is a hydrolysis-condensation catalyst, The resin composition according to any one of claims 1 to 6 A method for manufacturing a product is provided.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which utilized each advantage of an epoxy resin and a silicone resin, was excellent in fluidity | liquidity, and the improvement of the storage stability was achieved.
Moreover, the sealing material which consists of the hardened | cured material of the said resin composition which has the outstanding light resistance and the thermal shock resistance, and also the hardened | cured material of the said resin composition is obtained.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described.
Note that the present invention is not limited to the present embodiment, and can be implemented with various modifications within the scope of the gist.

[Method for producing resin composition]
The method for producing a resin composition of the present embodiment includes a step of cohydrolyzing and condensing (A) an epoxy resin and an alkoxysilane compound represented by the following formula (1). In the condensation, dehydration condensation of an intermediate having a condensation rate of 78% or more is performed.

In formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. Moreover, several R < ² > may be the same or different and shows a hydrogen atom or a C1-C8 alkyl group.

The alkoxysilane compound is
(B) n = 1 to 2, R ¹ having at least one cyclic ether group, and (C) n = 1 to 2, R ¹ being at least 1 The mixture index α of (B) and (C), which includes at least one alkoxysilane compound having one aryl group and is represented by the following formula (2), is 0.001 to 19.
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C))

The “cohydrolytic condensation” is composed of two steps, a reflux step without dehydration and a subsequent dehydration condensation step. The “condensation rate” is the condensation rate after passing through the refluxing step.
The “refluxing process without dehydration” is a process in which water and a solvent blended for cohydrolysis and water and a solvent derived from an alkoxysilane compound generated during the reaction are reacted while being returned to the reaction solution. is there. For example, a cooling tube is attached to the upper part of the reaction vessel, and the reaction is performed while refluxing the generated water and solvent.
The “dehydration condensation step” is a step in which the condensation reaction is performed while removing the blended water and solvent and the water and solvent generated in the “refluxing step without dehydration”. For example, the reaction is performed by distillation under reduced pressure using a rotary evaporator or the like.

In the present embodiment, the condensation rate of the intermediate is 78% or more. The condensation rate is preferably 80% or more, and more preferably cohydrolytic condensation under the condition of 83% or more.
If the condensation rate of the intermediate is less than 78%, many OH groups derived from silicone remain in the produced resin composition even after the subsequent dehydration condensation step, and the residual OH groups are condensed during storage. Doing so is not desirable because it causes remarkable thickening and gelation of the resin composition and deteriorates storage stability.

In the present embodiment, the resin composition is obtained by “cohydrolysis condensation”. “Cohydrolysis condensation” means a hydrolysis condensation reaction performed in the presence of an epoxy resin, and in the absence of an epoxy resin. The reaction in is clearly distinguished.
The heating temperature in the cohydrolysis condensation reaction step is preferably 130 ° C or lower, more preferably 0 to 120 ° C, and further preferably 0 to 100 ° C.
If it exceeds 130 ° C., the resin composition may be altered depending on the composition.
The reaction time for cohydrolysis condensation is preferably 0.5 to 24 hours, and more preferably 1 to 12 hours. If the reaction time is less than 0.5 hour, the remaining amount of unreacted substances may increase depending on the composition.

((A) Epoxy resin)
(A) The epoxy resin means a compound having an oxirane ring, usually two or more oxirane rings in the molecule, excluding an alkoxysilane compound and its condensate described later, and satisfying this condition. For example, there is no particular limitation.
Epoxy resins may be used alone or in combination.

(A) The epoxy equivalent (WPE) of the epoxy resin is preferably 100 to 600 g / eq, preferably 100 to 500 g / eq, and more preferably 100 to 300 g / eq.
Depending on the composition balance with the alkoxysilane compound represented by the formula (1), when the epoxy equivalent (WPE) is less than 100 g / eq, the storage stability of the target resin composition may be reduced, and 600 g If it exceeds / eq, the thermal shock resistance of the cured product of the resin composition may be deteriorated.
Although the use of the resin composition of this Embodiment and the hardened | cured material of a resin composition is not specifically limited, Especially when using as a sealing material, the epoxy equivalent of an epoxy resin is 100-300 g / eq. It is preferable that

The (A) epoxy resin is preferably a liquid having a viscosity at 25 ° C. of 1000 Pa · s or less, more preferably 500 Pa · s or less, and even more preferably 100 Pa · s or less.
When the viscosity at 25 ° C. exceeds 1000 Pa · s, the fluidity as a liquid is lost, and the compatibility with the alkoxysilane compound described later tends to deteriorate.
In addition, when the viscosity at 25 ° C. is more than 500 Pa · s and 1000 Pa · s or less (500 Pa · s <viscosity ≦ 1000 Pa · s), it can be used by adjusting the temperature at the time of production, selecting a solvent, etc. Since manufacturing conditions tend to be somewhat limited, it is preferably 500 Pa · s or less.

The type of epoxy resin is not particularly limited, and specific examples include polyfunctional epoxy resins that are glycidyl etherified products of polyphenol compounds, alicyclic epoxy resins, and polyfunctional epoxy that are glycidyl etherified products of various novolak resins. Examples thereof include resins, nuclear hydrides of aromatic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, and the like.
In particular, a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound, an alicyclic type, from the viewpoint that it is easily available and has good physical properties when the intended resin composition of the present embodiment is a cured product. Epoxy resins are preferred, and polyfunctional epoxy resins that are glycidyl etherified products of polyphenol compounds are more preferred.
These epoxy resins may be used alone or in combination.

(Polyfunctional epoxy resin)
The polyfunctional epoxy resin which is a glycidyl etherified product of a polyphenol compound is not particularly limited, and specifically, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethyl Bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl)- 2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene -Bis (3-methyl-6-tert-butyl) Ruphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 2,6-di (t-butyl) hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-di (4-hydroxyphenyl) fluorene, etc. Examples thereof include phenols having a fluorene skeleton, polyfunctional epoxy resins which are glycidyl etherified products of polyphenol compounds of phenolized polybutadiene.
Among the above, many of the types that are excellent in transparency and fluidity are commercially available, and are available at low cost, and excellent in thermal shock resistance when the target resin composition is cured. Since it tends to be a polyfunctional epoxy resin that is a glycidyl etherified product of phenols having a bisphenol A skeleton, it is preferable.

  Typical examples of polyfunctional epoxy resins that are glycidyl ethers of phenols having a bisphenol skeleton are given below.

(A) When using a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound as the epoxy resin, these repeating units (n in the chemical formula showing the above representative examples) are not particularly limited, Less than 50 is preferable, 0.001 to 5 is more preferable, and 0.01 to 2 is more preferable.
When the repeating unit is less than 0.001, the reactivity with the alkoxysilane compound may be deteriorated, and when it exceeds 50, the fluidity is lowered, which may cause a practical problem. Therefore, from the viewpoint of balance between reactivity and fluidity, the repeating unit is particularly preferably from 0.01 to 2.

(Alicyclic epoxy resin)
The alicyclic epoxy resin is not particularly limited as long as it is an epoxy resin having an alicyclic epoxy group, and examples thereof include an epoxy resin having a cyclohexene oxide group, a tricyclodecene oxide group, a cyclopentene oxide group, and the like. Can be mentioned.
Specific examples of the alicyclic epoxy resin include 4-vinyl epoxycyclohexane, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, and ETHB as monofunctional alicyclic epoxy compounds. Examples of the bifunctional alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4 -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methyl) (Cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethyl Glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexane carboxylate), 1,2,8,9- diepoxylimonene, and the like. Examples of the polyfunctional alicyclic epoxy compound include 1,2-epoxy-4- (2-oxiranyl) cyclohexene adduct of 2,2-bis (hydroxymethyl) -1-butanol. Examples of the polyfunctional alicyclic epoxy compound include Epolide GT300, GT400, EHPE3150, and the like.
A typical example of an alicyclic epoxy resin is shown below.

(Polyfunctional epoxy resin that is glycidyl etherified product of novolak resin)
The polyfunctional epoxy resin that is a glycidyl etherified product of novolak resin is not particularly limited, and examples thereof include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthol. Glycidyl etherified products of various novolac resins such as novolak resins made from various phenols such as chlorophenols, phenol novolak resins containing xylylene skeleton, phenol novolac resins containing dicyclopentadiene skeleton, biphenyl skeleton containing phenol novolac resins, fluorene skeleton containing phenol novolac resins Etc.
A typical example of a polyfunctional epoxy resin which is a glycidyl etherified product of a novolak resin is shown below.

(Nuclear hydride of aromatic epoxy resin)
The nuclear hydride of the aromatic epoxy resin is not particularly limited. For example, glycidyl etherified products of phenol compounds (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.) or various phenols (phenols) , Cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.) and hydrides of glycidyl ethers of novolac resins Can be mentioned.

(Aliphatic epoxy resin)
The aliphatic epoxy resin is not particularly limited, and specifically, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, xylylene glycol derivatives, etc. Examples thereof include glycidyl ethers of polyhydric alcohols.

(Heterocyclic epoxy resin)
The heterocyclic epoxy resin is not particularly limited, and examples thereof include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.

(Glycidyl ester epoxy resin)
The glycidyl ester-based epoxy resin is not particularly limited, and examples thereof include epoxy resins composed of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.

(Glycidylamine epoxy resin)
The glycidylamine epoxy resin is not particularly limited. For example, an epoxy resin obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative, and diaminomethylbenzene derivative. Etc.

(Epoxy resin obtained by glycidylation of halogenated phenols)
Epoxy resins obtained by glycidylation of halogenated phenols are not particularly limited. For example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated Examples thereof include epoxy resins obtained by glycidyl etherification of halogenated phenols such as bisphenol S and chlorinated bisphenol A.

The epoxy resin mentioned above can be used in combination with a polyol.
The polyol is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule. For example, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,2-hexanediol, 1,6- Examples include hexanediol.

(Alkoxysilane compound)
The alkoxysilane compound is a silicon compound having 1 to 4 alkoxyl groups, and is represented by the following general formula (1).

In formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group.
Moreover, several R < ² > shows a hydrogen atom or a C1-C8 alkyl group, and may mutually be same or different.

R ¹ represents an organic group and is not particularly limited. In addition to an organic group having a cyclic ether group and an organic group having an aryl group, which will be described later, for example, a hydrogen atom, an alkyl group, a vinyl group, methacryl Group, a mercapto group, an organic group having an isocyanate group, and the like, and an alkyl group is particularly preferable.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group (n-butyl, i-butyl, t-butyl, sec-butyl), a pentyl group (n-pentyl, i-pentyl, neopentyl etc.), hexyl group (n-hexyl, i-hexyl etc.), heptyl (n-heptyl, i-heptyl etc.), octyl group (n-octyl, i-octyl, t-octyl etc.), Nonyl (n-nonyl, i-nonyl, etc.), decyl group (n-decyl, i-decyl, etc.), dodecyl group (n-dodecyl, i-dodecyl, etc.) are mentioned, and these are linear or branched Any of these alkyl groups may be used.
In particular, an alkyl group having 10 or less carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group are more preferable.
In addition, hydrogen atoms or a part or all of the main chain skeleton of these alkyl groups are ether groups, ester groups, carbonyl groups, siloxane groups, halogen atoms such as fluorine, methacryl groups, acrylic groups, mercapto groups, amino groups, It may be substituted with at least one group selected from the group consisting of hydroxyl groups.

Moreover, several R < ² > in the said Formula (1) shows a hydrogen atom or a C1-C8 alkyl group, and may be same or different, respectively.
R ² is not particularly limited as long as it satisfies the above requirements, but a methyl group and an ethyl group are particularly preferable.

Incidentally, the formula (1) in the (OR ^2), instead of the hydroxyl group or an alkoxyl group having 1 to 8 carbon atoms, other hydrolyzable group (chlorine atom, an acetoxy group, an isopropenoxy group, amino group, etc.) The replacement may be used as (OR ² ).
Examples of such silane compounds include methyltrichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane and the like.

((B) component)
The component (B) of the alkoxysilane compound represented by the formula (1) is n = 1 to 2 in the formula (1), and R ¹ has at least one cyclic ether group. It is an alkoxysilane compound.
The cyclic ether group is an organic group having an ether in which carbon of a cyclic hydrocarbon is substituted with oxygen, and usually means a cyclic ether group having a 3- to 6-membered ring structure. Particularly, a 3-membered or 4-membered cyclic ether group having a large ring strain energy and high reactivity is preferable, and a 3-membered ether group is particularly preferable.

Examples of the cyclic ether group include glycidoxyalkyl groups, glycidyl groups, β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl, and other glycidoxyalkyl groups, glycidyl groups, β -(3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4 epoxyepoxycyclohexyl) propyl group An alkyl group substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as β- (3,4-epoxycyclohexyl) butyl group and β- (3,4-epoxycyclohexyl) pentyl group. Can be mentioned.
Among these, in particular, a glycidyl group bonded to a C1-C3 alkyl group such as β-glycidoxyethyl group, γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, and the like. An alkyl group having 3 or less carbon atoms substituted with a C5-C8 cycloalkyl group having a sidoxyalkyl group or an oxirane group is preferred.

Examples of the component (B) include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3-epoxypropyl (Phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ) Ethyl triethoxysilane, 2,3-epoxypropyl trimethoxysilane, 2,3-epoxy propyl triethoxy silane, and the like.
These may be used alone or in combination of two or more.

((C) component)
The component (C) of the alkoxysilane compound represented by the formula (1) is at least one alkoxy having n = 1 to 2 and having at least one aryl group as R ¹ in the formula (1). Silane compound.

An aryl group means a functional group or substituent derived from an aromatic hydrocarbon (simple aromatic ring or polycyclic aromatic hydrocarbon).
The aryl group is not particularly limited as long as it matches this, but in consideration of steric hindrance in the higher order structure, a phenyl group, a benzyl group, and the like are preferable.

  Examples of the component (C) include dimethoxymethylphenylsilane, diethoxymethylphenylsilane, phenyltriethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, dimethoxydiphenylsilane, diphenyldiethoxysilane, and phenyltrimethoxysilane. N-phenyl-3-aminopropyltrimethoxysilane and the like. These may be used alone or in combination of two or more.

"(B) component: In formula (1), n = 1 to 2, and at least one cyclic silane group having at least one cyclic ether group as R ¹ " and "(C) component" : In formula (1), n = 1 to 2 and R ¹ has at least one aryl group, and the mixing ratio with “at least one alkoxysilane compound” is calculated by the following formula (2). It is represented by a mixing index α.
Mixing index α = (αc) / (αb) (2)
(Wherein, αb: mol% of component (B), αc: mol% of component (C)).
The mixing index α of component (B) / component (C) is in the range of 0.001-19.
When the mixing index α is less than 0.001, the fluidity and storage stability of the resin composition in the present embodiment are reduced, and when it exceeds 19, the fluidity of the resin composition in the present embodiment and the cured product Thermal shock resistance deteriorates. In particular, when considering use in a sealing material application, since a high thermal shock resistance is required, the mixing index α is preferably 0.2 to 5, and preferably 0.3 to 2. It is more preferable.

((D) component)
In the resin composition of this embodiment, in addition to the components (A) to (C) described above, as a compound represented by the formula (1), n indicating the number of R ¹ in the formula (1) is n = An alkoxysilane compound having 0, that is, four (OR ² ) may be further added to carry out cohydrolysis condensation.
Examples of the component (D) include tetramethoxysilane and tetraethoxysilane. These may be used alone or in combination.

(Other alkoxysilane compounds)
In the resin composition of the present embodiment, in addition to the components (B) to (D) described above, an alkoxysilane compound represented by the formula (1) may be further added and cohydrolyzed and condensed.
Examples of such compounds include dimethyldimethoxysilane, dimethylethoxysilane, hydroxymethyltrimethylsilane, methoxytrimethylsilane, methyltrimethoxysilane, mercaptomethyltrimethoxysilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, bis (2-chloro Ethoxy) methylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethyltriethoxysilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, ethoxydimethylvinylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxymethylsilane , Methyltris (ethylmethylketoxime) silane, trimethylpropoxysilane, trimethoxyisopropoxysilane, diethoxydi Tilsilane, 3- [dimethoxy (methyl) silyl] propane-1-thiol, trimethoxy (propyl) silane, (3-mercaptopropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, diethoxymethylvinylsilane, butoxytrimethylsilane, Butyltrimethoxysilane, methyltriethoxysilane, methoxyltriethoxysilane, triethoxyvinylsilane, diethoxydiethylsilane, dimethoxyldipropoxysilane, ethyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane Allyltriethoxysilane, 3-bromopropyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, hexyloxytrimethylsilane, propyltriethoxysilane, Xyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3-ureidopropyltriethoxysilane, Methoxytripropylsilane, dibutoxydimethylsilane, methyltripropoxysilane, methyltriisopropoxysilane, octyloxytrimethylsilane, pentyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, hexyltriethoxysilane, Examples include 3-methacryloxypropyltriethoxysilane, octyltriethoxysilane, dodecyloxytrimethylsilane, and diethoxydodecylmethylsilane.

Among the alkoxysilane compounds used in the method for producing the resin composition of the present embodiment, “n = 2 alkoxysilane compound”, “n = 1 alkoxysilane compound”, and “n = 0 alkoxysilane”. The mixing ratio of “compound” is represented by a mixing index β calculated by the following formula (3).
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
In the above formula (3),
β ⁿ² : content (mol%) of an alkoxysilane compound in which n = 2 in formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n = 1 in formula (1),
And 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1.
In the present embodiment, the mixing index β is preferably 0.01 to 1.4, more preferably 0.03 to 1.2, and still more preferably 0.05 to 1.0.
When the mixing index β is less than 0.01, the fluidity of the produced resin composition tends to deteriorate, and when it exceeds 1.4, the thermal shock resistance tends to deteriorate.

In the present embodiment, the mixing ratio of (A) the epoxy resin and the “alkoxysilane compound where n = 0 to 2” among the alkoxysilane compounds is represented by a mixing index γ calculated by the following formula (4). The
Mixing index γ = (γa) / (γs) (4)
In the above formula (4),
γa: mass of epoxy resin (g),
γs: represents the mass (g) of the alkoxysilane compound in which n = 0 to 2 in the general formula (1).
In the resin composition of the present embodiment, the mixing index γ is preferably 0.02 to 15, more preferably 0.04 to 7, and still more preferably 0.08 to 5.
When the mixing index γ is less than 0.02, when the resin composition is a cured product, the adhesion as the cured product may be deteriorated or the hardness may be decreased. May get worse.

(Hydrolysis condensation catalyst)
In the present embodiment, a hydrolysis-condensation catalyst may be added during the above-described (A) step of co-hydrolysis condensation of the epoxy resin and the alkoxysilane compound.
The hydrolysis condensation catalyst is not particularly limited as long as it promotes a conventionally known hydrolysis condensation reaction. For example, a metal (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth, etc., organic metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium) Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth and other organic oxides, organic acid salts, organic halides, alkoxides, etc.), inorganic bases Magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.), organic base (Ammonia, tetramethylammonium hydroxide, etc.).

Among the above organic metals, organic tin is preferable.
Organic tin means that at least one organic group is bonded to a tin atom, and examples of the structure include monoorganotin, diorganotin, triorganotin, and tetraorganotin.
Examples of the organic tin include tin tetrachloride, monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra n-octyltin, tetra n-butyltin, dibutyltin oxide, dibutyltin diacetate, dibutyltin dioctate, dibutyl Tin diversate, dibutyltin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin / silicon ethyl reactant, dibutyltin salt and silicate compound, dioctyltin salt and silicate compound, dibutyltin bis ( Acetylacetonate), dibutyltin bis (ethyl malate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis (benzylmalate), dibutyltin bis Allyl malate), dibutyltin bis (oleylmalate), dibutyltin malate, dibutyltin bis (O-phenylphenoxide), dibutyltin bis (2-ethylhexylmercaptoacetate), dibutyltin bis (2-ethylhexylmercaptopropionate) Dibutyltin bis (isononyl 3-mercaptopropionate), dibutyltin bis (isooctylthioglycolate), dibutyltin bis (3-mercaptopropionate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, Dioctyltin dioctate, dioctyltin didodecyl mercapto, dioctyltin versatate, dioctyltin distearate, dioctyltin bis (ethyl malate), dioctyltin bis (octylmalate), dioctyl Rutin malate, dioctyltin bis (isooctylthioglycolate), dioctyltin bis (2-ethylhexyl mercaptoacetate), dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethoxide, dioctyltin dibutoxide, Examples include tin octylate and tin stearate.

Among the above organic metals, an alkali organic metal that exhibits alkalinity when a ligand is liberated is preferable. By using an alkaline organic metal as the hydrolysis condensation catalyst, the storage stability of the resin composition of the present embodiment can be improved.
By using an alkali organic metal, the progress of the condensation reaction is accelerated, so that it is very useful for obtaining a resin composition having a reflux upcondensation rate of 78% or more.
Among the alkali organic metals, alkali organic tin is preferable, and alkoxide organic tin is particularly preferable. For example, dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethyloxide, dioctyltin dibutoxide and the like can be mentioned.
On the other hand, when a ligand is liberated, if an acid-based organic metal that shows acidity is used as a hydrolysis-condensation catalyst, the hydrolysis reaction is performed quickly, but the condensation reaction tends to be difficult to proceed. It is not preferable for practical use.
The hydrolytic condensation catalysts described above may be used alone or in combination of two or more.
For example, organic acid tin and alkaline organic tin may be used in combination, or may be treated with an inorganic base after reacting with an organic acid salt such as tin. In this case, the inorganic base is preferably a hydroxide of a polyvalent cation such as magnesium hydroxide, calcium hydroxide, strontium hydroxide or barium hydroxide.

The addition amount of the hydrolysis condensation catalyst described above is not particularly limited, but the preferable addition amount is obtained from the following mixing index δ which is a ratio to (OR ² ) in the above formula (1).
The mixing index δ is expressed by the following formula (5).
Mixing index δ = (δe) / (δs) (5)
In formula (5),
δe: addition amount of hydrolysis condensation catalyst (mol number)
δs: amount (mol number) of (OR ² ) in the above formula (1)
Respectively.
The mixing index δ is preferably 0.0005 to 5, more preferably 0.001 to 1, and further preferably 0.005 to 0.5.
Depending on the composition of the resin composition, if the mixing index δ is less than 0.0005, the effect of promoting hydrolysis condensation may be difficult to obtain. If it exceeds 5, the ring opening of the cyclic ether group may be promoted. This is not preferable because storage stability may be deteriorated.

In the step of obtaining the resin composition by cohydrolysis condensation, the preferred amount of water added is determined from the mixing index ε, which is the ratio to (OR ² ) in the above formula (1).
The mixing index ε is expressed by the following formula (6).
Mixing index ε = (εw) / (εs) (6)
In formula (6),
εw: amount of water added (in mol),
εs: Indicates the amount (mol number) of (OR ² ) in the general formula (1).
The mixing index ε is preferably 0.1 to 5, more preferably 0.2 to 3, and still more preferably 0.3 to 1.5.
If the mixing index ε is less than 0.1, the hydrolysis reaction may not proceed. If it exceeds 5, the storage stability of the resin composition may be deteriorated, which is not preferable.
The addition of water in the co-hydrolysis condensation described above is mainly performed by hydrolysis of the alkoxysilane compound, and therefore needs to be performed in the “refluxing process without dehydration”. The timing of the addition is not particularly limited, and may be added first, or may be gradually added during the reaction using a feed pump or the like.

The above-mentioned cohydrolytic condensation may be performed without a solvent or in a predetermined solvent.
In the case of using a solvent, a known one can be used as long as it is an organic solvent that can dissolve the epoxy resin and the alkoxysilane compound and is inactive to them.
As the solvent, for example, aprotic polar solvents such as tetrahydrofuran and dioxane are suitable. Moreover, since it is easy to obtain, alcohol solvents such as methanol, ethanol, butanol, isopropanol, and n-butanol can be used. However, these promote the ring opening of the epoxy group. May not be suitable for use.

The addition amount of the solvent is preferably 0.01 to 20 times, more preferably 0.02 to 15 times the total mass of the epoxy resin and the alkoxysilane compound subjected to the cohydrolysis condensation reaction. The amount of 0.03 to 10 times is more preferable.
Since the molecular weight of the resin composition of the present embodiment can be controlled by the addition amount of the solvent, a resin composition having an appropriate molecular weight and thus an appropriate viscosity can be obtained by setting the addition amount in the above range.

The resin composition obtained in the present embodiment may further contain a predetermined (F) curing agent and (G) curing accelerator.
(F) The curing agent and (G) the curing accelerator will be described below.

(Curing agent)
A hardening | curing agent is a substance used in order to harden a resin composition, and is not specifically limited.
As the cured product, for example, an acid anhydride compound, an amine compound, an amide compound, a phenol compound, etc. can be used, and in particular, an aromatic acid anhydride, a cyclic aliphatic acid anhydride, an aliphatic acid anhydride, etc. An acid anhydride compound is preferred, and a carboxylic acid anhydride is more preferred.
The acid anhydride compounds include alicyclic acid anhydrides, and alicyclic carboxylic acid anhydrides are preferred among the carboxylic acid anhydrides. These hardened | cured materials may be used individually or may be used in combination of 2 or more type.
Specific examples of the curing agent include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride. , Methylhexahydrophthalic anhydride, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, tetraethylenepentamine, dimethylbenzylamine, ketimine compound, linolenic acid dimer and ethylenediamine Polyamide resin, bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc. Biphenols such as polycondensates of aldehydes with various aldehydes, polymers of phenols with various diene compounds, polycondensates of phenols with aromatic dimethylol, or condensates of bismethoxymethylbiphenyl with naphthols or phenols And modified products thereof, imidazole, boron trifluoride-amine complex, guanidine derivatives and the like.
Specific examples of the alicyclic carboxylic acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, “4-methylhexahydro Phthalic anhydride / hexahydrophthalic anhydride = 70/30 ”, 4-methylhexahydrophthalic anhydride,“ methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride / bicyclo [2.2. 1] heptane-2,3-dicarboxylic anhydride "and the like.

The addition amount of the curing agent is obtained from the mixed index ζ which is a ratio to the cyclic ether group contained in the above-described epoxy resin and alkoxysilane compound.
The mixing index ζ is expressed by the following formula (7).
Mixing index ζ = (ζf) / (ζk) (7)
In formula (7),
ζf: addition amount (number of moles) of curing agent,
ζk: Indicates the amount (mol number) of cyclic ether groups contained in the epoxy resin and the alkoxysilane compound.
The mixing index ζ is preferably 0.1 to 1.5, more preferably 0.2 to 1.3, and still more preferably 0.3 to 1.5.
If the mixing index ζ is less than 0.1, the curing rate may decrease, and if it exceeds 1.5, the moisture resistance as a cured product may deteriorate.

(Curing accelerator)
A curing accelerator is a curing catalyst used for the purpose of promoting the curing reaction.
As the curing accelerator, tertiary amines and salts thereof are preferable.
Specific examples of the curing accelerator include those shown in the following (1) to (8).
(1) Tertiary amines: benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine and the like.
(2) Imidazoles: 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-un Decylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl -4,5-di (hydroxymethyl) imidazole, 1- (2- Anoethyl) -2-phenyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) ) -2-Phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′) )] Ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methyl Imidazolyl- (1 ′)] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-dia Roh-6- [2'-methylimidazolyl- - (1 &apos;)] isocyanuric acid adduct of ethyl -s- triazine.
(3) Organophosphorus compounds: diphenylphosphine, triphenylphosphine, triphenyl phosphite and the like.
(4) Quaternary phosphonium salts: benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphos Phonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n- Butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphenol Scan follower tetra Tsu tetraphenylborate and the like.
(5) Diazabicycloalkenes: 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof.
(6) Organometallic compounds: zinc octylate, tin actylate, aluminum acetylacetone complex, and the like.
(7) Quaternary ammonium salts: tetraethylammonium bromide, tetra-n-butylammonium bromide and the like.
(8) Metal halide compounds: Boron compounds such as boron trifluoride and triphenyl borate; zinc chloride, stannic chloride and the like.

The addition amount of a hardening accelerator is calculated | required from the following mixing parameter | index (eta) which is a ratio with respect to the mass of the above-mentioned epoxy resin and alkoxysilane compound.
The mixing index η is represented by the following formula (8).
Mixing index η = (ηg) / (ηk) (8)
In formula (8),
ηg: mass (g) of curing accelerator,
ηk: mass (g) of epoxy resin and alkoxysilane compound.
The mixing index η is preferably 0.01 to 5, more preferably 0.05 to 3, and further preferably 0.1 to 1.
If the mixing index η is less than 0.01, curing may not proceed well, and if it exceeds 5, the cured product may be colored.

[Cured product]
The cured product is obtained by curing the resin composition obtained by the above-described production method of the present embodiment by applying heat or energy rays. Particularly preferred is thermosetting.

First, thermosetting will be described.
Thermal curing is a method of obtaining a cured product by causing a chemical reaction by heat and generating three-dimensional cross-linking between molecules.
Examples of the thermosetting method include a method in which the resin composition contains a curing agent and a curing accelerator and heat-treats the resin composition, and a method in which the resin composition is thermally cured using a thermal cationic polymerization initiator. In particular, a method of heat-treating a curing agent or a curing accelerator in advance is preferable.

(Thermal cationic polymerization initiator)
The thermal cationic polymerization initiator is a compound that initiates polymerization by generating cationic species by heat. Examples thereof include various onium salts such as quaternary ammonium salts, sulfonium salts, phosphonium salts, and aromatic onium salts. These may be used alone or in combination of two or more. Although the usage method is not particularly limited, a method in which a thermal cationic polymerization initiator is contained in the resin composition and heat-treated is generally used.

  Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium-p-toluenesulfonate, N, N-dimethyl. -N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyl Trifluoromethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-diethyl N-(4-methoxybenzyl) preparative Luigi hexafluoroantimonate and the like.

  Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsinate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, diphenyl (4-phenylthiophenyl). ) Sulfonium hexafluoroarsinate and the like.

  Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

  As specific examples of the aromatic onium salt, compounds exemplified in Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-14278, Japanese Patent Publication No. 52-14279, and the like can be used.

Next, energy beam curing will be described.
The energy ray curing is a cured product by irradiating the resin composition of this embodiment with predetermined energy rays (in addition to light such as ultraviolet rays, near ultraviolet rays, visible light, near infrared rays, and infrared rays, electron beams, etc.). Is the way to get.
As the energy ray, light is preferable, and ultraviolet light is more preferable.
Sources of energy rays include, for example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, UV lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser. And various light sources such as a helium neon laser, a krypton ion laser, various semiconductor lasers, a YAG laser, an excimer laser, a light emitting diode, a CRT light source, a plasma light source, and an electron beam irradiator.
In the energy ray curing step, the polymerization initiator added to the resin composition is decomposed by energy ray stimulation to generate a polymerization initiating species, the polymerizable functional group of the target substance is polymerized, and curing proceeds.

The polymerization initiators can be roughly classified into the following three (1) to (3) depending on the generated active species.
These polymerization initiators may be used alone or in combination of two or more.
(1) Those that generate radicals upon irradiation with energy rays.
(2) Those that generate cations by irradiation with energy rays (when the energy rays are light, they are called photoacid generators).
(3) Those that generate anions upon irradiation with energy rays (referred to as photobase generators when the energy rays are light).

  Examples of polymerization initiators used for energy ray curing include benzoins and benzoin alkyl ethers (benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, etc.), and acetophenones (acetophenone, 2,2-dimethoxy-2-phenyl). Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-monoforino-propane-1- ON, N, N-dimethylaminoacetophenone, etc.), anthraquinones (2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylan Laquinone, 2-aminoanthraquinone, etc.), thioxanthones (2,4-dimethylthiosantone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.), ketals (acetophenone dimethyl ketal, benzyldimethyl) Ketones, etc.), benzophenones (benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, etc.), xanthones, benzoates (ethyl 4-dimethylaminobenzoate, 2- (dimethyl) Amino) ethyl benzoate, etc.), amines (triethylamine, triethanolamine, etc.), iodonium salt compounds, sulfonium salt compounds, ammonium salt compounds, phosphonium salt compounds, al Salt compounds, stibonium salt compound, an oxonium salt compound, a selenonium salt compound, a stannonium salt compound and the like.

(Additive for resin composition and cured product)
In the resin composition of the present embodiment and the cured product thereof, various organic resins, inorganic fillers, colorants, leveling agents, lubricants, surfactants, silicone-based resins are used as long as their functions are not impaired. A compound, a reactive diluent, a non-reactive diluent, an antioxidant, a light stabilizer and the like can be added as appropriate. In addition, plasticizers, flame retardants, stabilizers, antistatic agents, impact strengthening agents, foaming agents, antibacterial / antifungal agents, conductive fillers, antifogging agents, and crosslinks that are generally used as additives for resins An agent or the like can be blended.

  The organic resin is not particularly limited, and examples thereof include an epoxy resin, an acrylic resin, a polyester resin, and a polyimide resin. In particular, those having highly reactive organic groups such as epoxy resins are preferred.

  Examples of inorganic fillers include silicas (melted crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.) silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, sulfuric acid Barium, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber And molybdenum disulfide. In particular, silicas, calcium carbonate, aluminum oxide, aluminum hydroxide, calcium silicate and the like are preferable, and silicas are more preferable in consideration of physical properties of the cured product. These inorganic fillers may be used alone or in combination of two or more.

  The colorant is not particularly limited as long as it is a substance used for the purpose of coloring. For example, phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, azomethine series Inorganic pigments such as titanium oxide, lead sulfate, chromium yellow, zinc yellow, chromium vermillion, valve shell, cobalt purple, bitumen, ultramarine, carbon black, chromium green, chromium oxide, cobalt green, and the like. These colorants may be used alone or in combination of two or more.

  The leveling agent is not particularly limited, and examples thereof include oligomers having a molecular weight of 4000 to 12000 made of acrylates such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, Examples include hydrogenated castor oil and titanium-based coupling agents. These leveling agents may be used alone or in combination of two or more.

  The lubricant is not particularly limited, and examples thereof include hydrocarbon lubricants such as paraffin wax, microwax, and polyethylene wax, and higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. Lubricants, stearylamide, palmitylamide, oleylamide, higher fatty acid amide lubricants such as methylene bisstearamide, hardened castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono- , Di-, tri-, or tetra-) stearate and other higher fatty acid ester lubricants, cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol and other alcohol lubricants, lauric acid, myristic acid, palmitic Natural waxes such as metal soaps such as magnesium, calcium, cadmium, barium, zinc, lead, etc., such as acid, stearic acid, arachidic acid, behenic acid, ricinoleic acid, naphthenic acid, carnauba wax, candelilla wax, beeswax, montan wax And the like. These lubricants may be used alone or in combination of two or more.

  The surfactant is an amphiphilic substance having a hydrophobic group having no affinity for the solvent in the molecule and an amphiphilic group (usually a hydrophilic group) having an affinity for the solvent. The type of the surfactant is not particularly limited, and examples thereof include silicone surfactants and fluorine surfactants. Surfactants may be used alone or in combination of two or more.

  The silicone compound is not particularly limited, and examples thereof include silicone resin, silicone condensate, silicone partial condensate, silicone oil, silane coupling agent, silicone oil, polysiloxane and the like. These may be modified by introducing organic groups into both ends, one end, or side chains. The modification method is not particularly limited. For example, amino modification, epoxy modification, alicyclic epoxy modification, carbinol modification, methacryl modification, polyether modification, mercapto modification, carboxyl modification, phenol modification, silanol modification, Examples include polyether modification, polyether / methoxy modification, and diol modification.

  The reactive diluent is not particularly limited. For example, alkyl glycidyl ether, alkylphenol monoglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, alkanoic acid glycidyl ester, ethylene Examples include glycol diglycidyl ether and propylene glycol diglycidyl ether.

  The non-reactive diluent is not particularly limited, and examples thereof include high-boiling solvents such as benzyl alcohol, butyl diglycol, and propylene glycol monomethyl ether.

  The antioxidant is not particularly limited, and examples thereof include organic phosphorus antioxidants such as triphenyl phosphate and phenylisodecyl phosphite, and organic sulfurs such as distearyl-3,3′-thiodipropinate. Examples of the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol.

  The light stabilizer is not particularly limited, and examples thereof include benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, and triazine-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.

You may add the following substance further to the resin composition produced by the manufacturing method of this embodiment, and its hardened | cured material.
For example, solvents, oils and fats, processed oils, natural resins, synthetic resins, pigments, dyes, pigments, release agents, preservatives, adhesives, deodorants, flocculants, cleaning agents, deodorants, pH adjusters, photosensitive materials, Ink, electrode, plating solution, catalyst, resin modifier, plasticizer, softener, agrochemical, insecticide, fungicide, pharmaceutical raw material, emulsifier / surfactant, rust inhibitor, metal compound, filler, cosmetic / pharmaceutical raw material , Dehydrating agent, drying agent, antifreeze, adsorbent, colorant, rubber, foaming agent, colorant, abrasive, mold release agent, flocculant, antifoaming agent, curing agent, reducing agent, flux agent, film treatment agent, Casting raw materials, minerals, acids / alkalis, shot agents, antioxidants, surface coating agents, additives, oxidants, explosives, fuels, bleaches, light emitting elements, fragrances, concrete, fibers (carbon fibers, aramid fibers, glass) Fiber), glass, metal, excipient, disintegrant, Mixture, fluidizing agents, gelling agents, stabilizers, preservatives, buffering agents, suspending agents, thickeners, and the like.

[Use of resin composition and cured product]
The resin composition obtained by the production method of the present embodiment and the cured product thereof can be used in various fields.
For example, electronic materials (such as insulators, AC transformers, switchgears and circuit units, package of various parts, IC / LED / semiconductor sealing materials, generators, motors and other rotating machine coils, windings, etc. Impregnation, printed wiring board, glass substitute transparent substrate, insulation board, medium-sized insulators, coils, connectors, terminals, various cases, electrical parts, etc.), paint (corrosion-resistant paint, maintenance, ship paint, corrosion-resistant lining, automobile / Primer for household appliances, beverage / beer can, outer surface lacquer, extrusion tube coating, general anti-corrosion coating, maintenance halfway, wood product lacquer, automotive electrodeposition primer, other industrial electrodeposition coating, beverage / beer can inner surface lacquer, Coil coating, drum / can inner coating, acid-resistant lining, wire enamel, insulating paint, automotive primer, various gold Appearance and anti-corrosion coating of products, pipe inner and outer surface coating, electrical parts insulation coating, etc.), composite materials (pipes and tanks for chemical plants, aircraft materials, automobile parts, various sports equipment, carbon fiber composite materials, aramid fiber composite materials) Etc.), civil engineering and building materials (floor materials, paving materials, membranes, anti-slip and thin pavement, concrete jointing / raising, anchor embedding adhesion, precast concrete bonding, tile adhesion, crack repair of concrete structures, pedestal grout・ Leveling, corrosion protection and waterproofing of water and sewage facilities, corrosion resistant laminated lining of tanks, anticorrosion coating of iron structures, mastic coating of exterior walls of buildings, etc., adhesives (metal, glass, ceramics, cement concrete, wood, plastic) Adhesives of the same or different materials such as, adhesives for assembly of automobiles, railway vehicles, aircraft, etc. Adhesives for manufacturing composite panels, etc .: Including one-part, two-part, and sheet types), aircraft / automobile / plastic molding jigs (resin molds such as press dies, stretched dies, matched dies, vacuum forming / blowing) Molds for molding, master models, casting patterns, laminated jigs, jigs for various inspections, etc.), modifiers and stabilizers (fiber resin processing, stabilizers for polyvinyl chloride, additives to synthetic rubber, etc.) Can be used as etc.

[Encapsulant]
The resin composition obtained by the production method of the present embodiment and its cured product are useful as a sealing material.
The sealing material is a member having a function of protecting a predetermined target from factors (foreign substances) such as temperature, humidity, and dust mainly in an airtight and liquidtight state. Foreign materials include sound, vibration, and erosion by chemical materials.
The sealing material can be used in combination with other sealing materials made of epoxy resin, silicone resin, epoxy silicone resin, acrylic resin, urethane resin, urea resin, imide resin, glass or the like.
The encapsulant is useful mainly for semiconductor applications, light emitting diode (LED) applications, and liquid crystal applications. In other words, it is used as a semiconductor encapsulant for protecting semiconductors from temperature, moisture, dust, etc., an LED encapsulant for protecting LEDs and extending their durability life, and a liquid crystal encapsulant for protecting liquid crystals In particular, it has high utility as an LED sealing material.

An LED is a semiconductor element that emits light when a voltage is applied in the forward direction. As a light emission principle, an electroluminescence (EL) effect is used.
Applications of LED sealing materials include, for example, displays, light-emitting display boards, traffic lights, display backlights (organic EL displays, mobile phones, mobile PCs, etc.), automobile interior / exterior certification, illumination, lighting equipment, flashlights, etc. Can be expanded to a wide range of fields.
About the use site | part of a LED sealing material, the case where it uses for protection of the junction part of a LED chip main body, a LED chip, a wire, and a lead wire etc. is mentioned, for example.
It can also be used in a lead-free reflow mounting process corresponding to the RoHS directive, which is becoming the mainstream instead of the conventional lead solder process.
Furthermore, you may mix | blend a predetermined | prescribed fluorescent substance with the sealing material of LED mentioned above. Thus, by absorbing light emitted from the light emitting element and performing wavelength conversion, an LED having a color tone different from the color tone of the light emitting element can be provided at the site of the sealing material.
The shape of the LED is not particularly limited, and can be appropriately selected according to the application. For example, a shell type, a surface mount type, a plate shape, a thin film shape and the like can be mentioned.

Moreover, the resin composition obtained by this embodiment and its hardened | cured material can be utilized besides the said sealing material.
For example, semiconductor / LED peripheral materials (lens materials, substrate materials, die bond materials, chip coating materials, laminated plates, optical fibers, optical waveguides, optical filters, adhesives for electronic components, coating materials, sealing materials, insulating materials, photoresists) , Encap materials, potting materials, light transmission layers and interlayer insulation layers of optical disks, printed wiring boards, laminates, light guide plates, antireflection films, etc.).
Examples of the lens material include a lens for an optical device, a lens for an automobile lamp, a spectacle lens, a pickup lens such as a CD / DVD, and a lens for a projector.

Examples of the present invention and comparative examples will be specifically described below.
First, evaluation methods of physical properties in Examples and Comparative Examples are shown below.

<Epoxy equivalent (WPE)>
It was measured according to “JIS K 7236: 2001 (How to determine epoxy equivalent of epoxy resin)”.
<Viscosity>
Measurement was performed under the following conditions.
Rotating E-type viscometer: “TV-22” manufactured by Toki Sangyo Co., Ltd.
Rotor: 3 ° × R14 (Other rotors may be selected as necessary.)
Measurement temperature: 25 ° C
Sample volume: 0.4mL

<Calculation of mixing index α>
The mixing index α was calculated from the following formula (2).
Mixing index α = (αc) / (αb) (2)
αb: (B) In formula (1), n = 1 to 2, and R ¹ is an alkoxysilane compound content (mol%) having at least one cyclic ether group.
αc: (C) The content (mol%) of an alkoxysilane compound having n = 1 to 2 and having at least one aryl group as R ¹ in formula (1).

<Calculation of mixing index β>
The mixing index β was calculated from the following formula (3).
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
β ⁿ² : Content of the alkoxysilane compound in which n = 2 in the general formula (1) (mol%)
β ⁿ⁰ : Content of the alkoxysilane compound in which n = 0 in the general formula (1) (mol%)
β ⁿ¹ : Content (mol%) of the alkoxysilane compound in which n = 1 in the general formula (1)
At this time, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1.

<Calculation of intermediate condensation rate>
The condensation rate of the intermediate was determined by the following procedure from the Si-NMR measurement result of the sample solution (intermediate) collected after the refluxing step.
(1) Preparation of Cr solution: Chloroform-d (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 6.3% by mass of Chromium (III) aceticlate (manufactured by Sigma-Aldrich) and dissolved.
(2) The sample solution after completion of the reflux process of 200 mg was weighed into a sample bottle, and the Cr solution was added to adjust to 1 g.
(3) The solution of (2) was transferred to an NMR tube having a diameter of 5 mmφ, and Si-NMR was measured under the following conditions.
Fourier transform nuclear magnetic resonance apparatus: “α-400 type” manufactured by JEOL Ltd.,
Nuclide: Si,
Integration count: 4000 times (4) The condensation rate K of the intermediate was determined according to the following formula.
Intermediate condensation rate K (%) = (D1 × 1 + D2 × 2 + T1 × 1 + T2 × 2 + T3 × 3) / {(D0 + D1 + D2) × 2 + (T0 + T1 + T2 + T3) × 3} × 100 (10)
Here, D0: the sum of integral values of signals derived from the D0 structure shown in the following formula (11) derived from the alkoxysilane compound in which n = 1 in the formula (1).
D1: Total of integral values of signals derived from the D1 structure shown in the following formula (12) derived from the alkoxysilane compound in which n = 1 in the formula (1).
D2: Sum of integral values of signals derived from the D2 structure shown in the following formula (12) derived from the alkoxysilane compound in which n = 1 in the formula (1).
T0: Total of integral values of T0 structure-derived signals represented by the following formula (13) derived from alkoxysilane compounds with n = 2 in formula (1).
T1: Total of integral values of signals derived from the T1 structure shown in the following formula (14) derived from the alkoxysilane compound in which n = 2 in the formula (1).
T2: Total of integral values of signals derived from the T2 structure shown in the following formula (14) derived from the alkoxysilane compound in which n = 2 in the formula (1).
T3: Total of integral values of signals derived from the T3 structure shown in the following formula (14) derived from the alkoxysilane compound in which n = 2 in the formula (1).

  In said Formula (11), R is arbitrary organic groups or H.

  In said formula (12), R is arbitrary organic groups or H.

  In the formula (13), R is any organic group or H.

  In said formula (14), R is arbitrary organic groups or H.

<Calculation of mixing index γ>
The mixing index γ was calculated from the following formula (4).
Mixing index γ = (γa) / (γs) (4)
γa: mass (g) of epoxy resin.
γs: Mass (g) of alkoxysilane compound in which n = 0 to 2 in formula (1).

<Calculation of mixing index δ>
The mixing index δ was calculated from the following formula (5).
Mixing index δ = (δe) / (δs) (5)
δe: addition amount of hydrolytic condensation catalyst (mol number).
δs: the amount (mol number) of (OR ² ) in the formula (1).

<Calculation of mixing index ε>
The mixing index ε was calculated from the following formula (6).
Mixing index ε = (εw) / (εs) (6)
here,
εw: amount of water added (in mol),
.epsilon.s: The amount (mol number) of (OR ²⁾ in formula (1).

<Calculation of mixing index ζ>
The mixing index ζ was calculated from the following formula (7).
Mixing index ζ = (ζf) / (ζk) (7)
here,
ζf: addition amount (number of moles) of curing agent,
ζk: The amount (mol number) of cyclic ether groups contained in the epoxy resin and the alkoxysilane compound.

<Calculation of mixing index η>
The mixing index η was calculated from the following formula (8).
Mixing index η = (ηg) / (ηk) (8)
here,
ηg: mass (g) of curing accelerator,
ηk: mass (g) of epoxy resin and alkoxysilane compound.

<Calculation of storage stability index θ and storage stability of resin composition>
The storage stability in the resin composition was evaluated by a storage stability index θ represented by the following formula (9).
Storage stability index θ = (storage viscosity) / (starting viscosity) (9)
The container containing the resin composition immediately after production was sealed and the temperature was adjusted at 25 ° C. for 2 hours, and then the viscosity at 25 ° C. was measured.
Further, the container containing the resin composition was sealed and stored in a constant temperature incubator at 60 ° C. for 16.5 days. After storage, the viscosity at 25 ° C. was measured, and this was designated as “storage viscosity”.
When the resin composition has fluidity (viscosity is 1000 Pa · s or less) and the storage stability index θ is 4 or less, it was judged to have storage stability.

<Light resistance test of cured product>
The light resistance of the cured product of the resin composition was evaluated by the following method.
(1) The cured product solution prepared by the method described later was cured to produce a cured product of 20 mm × 10 mm × thickness 3 mm.
(2) The cured product was covered with a black mask of 25 mm × 15 mm × thickness 1.2 mm with a hole having a diameter of 5.5 mm to obtain a sample for light resistance test.
(3) A UV irradiation device (USHIO INC., “Spot Cure SP7-250DB”) is connected to the sample in a constant temperature incubator at 50 ° C. via an optical fiber so that the sample can be irradiated with UV light. Got ready.
(4) The sample was set in a constant temperature incubator at 50 ° C. with the black mask on top.
(5) UV light of 2 W / cm ² was irradiated for 96 hours from the top of the black mask so that UV light could be irradiated to a hole with a diameter of 5.5 mm.
(6) The UV-irradiated sample was measured with a spectrocolorimeter (Nippon Denshoku Industries Co., Ltd., “SD5000”) with an integrating sphere opening modified to a diameter of 10 mm.
(7) Yellowness (YI) was determined according to “ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics”. When this YI was 13 or less, it was judged to have light resistance.

<Cold thermal shock test of cured product>
The thermal shock resistance of the cured product of the resin composition was evaluated by the following method.
(1) The following substrate and silicon chip were prepared.
(1-1) Substrate: “Amodel A-4122NL WH 905” manufactured by Solvay Advanced Polymers Co., Ltd. (having a recess of 10 mm in diameter and 1.2 mm in depth at the center of a flat plate of 15 mm × 15 mm × thickness 2 mm)
(1-2) Silicon chip (: A commercially available silicon wafer cut to 5 mm × 5 mm × thickness 200 μm)
(2) A solution for a cured product produced by the method described later was poured into the substrate, and 10 pieces of the silicon chip placed therein were produced and cured to obtain a thermal shock test sample.
(3) The above sample is set in a thermal shock device (manufactured by ESPEC Corporation, “TSE-11-A”), and “(−40 ° C. to 120 ° C.) / Cycle: exposure time 14 minutes, heating / cooling time 1 minute. The sample was heat cycled.
(4) The sample is taken out after 100 heat cycles, sprayed with a penetrating liquid (manufactured by Kosai Co., Ltd., “Microcheck”), and visually observed for abnormalities (peeling or cracks) under a magnifying glass. The number was recorded.
(5) Samples in which no abnormality was confirmed in the above (4) were put in the apparatus again, and evaluated by the same method over 100 heat cycles. These operations were repeated and evaluated.
(6) When abnormality was found in 2/10 samples, the evaluation was interrupted, and "number of cold shock resistance = (number of interrupted heat cycles)-(100 times)" was determined.
When the number of cold and thermal shock resistances was 100 times or more, it was judged that the cold and thermal shock resistance was practically sufficient.

Next, the raw materials used in Examples and Comparative Examples are shown in the following (1) to (9).
(1) Epoxy resin (1-1) Epoxy resin A: Poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as Bis-A epoxy resin)
・ Product name: “AER”, manufactured by Asahi Kasei Epoxy Corporation
Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
Epoxy equivalent (WPE): 187 g / eq
Viscosity (25 ° C.): 14.3 Pa · s
(1-2) Epoxy resin B: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate (hereinafter referred to as alicyclic epoxy resin)
・ Product name: “Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd.
Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
Epoxy equivalent (WPE): 131 g / eq
Viscosity (25 ° C.): 227 mPa · s

(2) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as GPTMS)
・ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
(3) Alkoxysilane compound I: phenyltrimethoxysilane (hereinafter referred to as PTMS)
・ Product name: “KBM-103” manufactured by Shin-Etsu Chemical Co., Ltd.
(4) Alkoxysilane compound J: Dimethyldimethoxysilane (hereinafter referred to as DMDMS)
・ Product name: “KBM-22” manufactured by Shin-Etsu Chemical Co., Ltd.
(5) Alkoxysilane compound K: tetraethoxysilane (hereinafter referred to as TEOS)
・ Product name: “KBE-04”, manufactured by Shin-Etsu Chemical Co., Ltd.

(6) Solvent (6-1) Tetrahydrofuran: Wako Pure Chemical Industries, Ltd., stabilizer-free type (hereinafter referred to as THF)
(6-2) tert-butanol: manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter referred to as t-BuOH)

(7) Hydrolytic condensation catalyst (7-1) Dibutyltin dimethoxide (hereinafter referred to as DBTDM): Sigma-Aldrich (7-2) Dioctyltin diacetate (hereinafter referred to as DOTDA): Nitto Kasei Co., Ltd. , "Neostan U-820"
(7-3) Dibutyltin dilaurate (hereinafter referred to as DBTDL): Wako Pure Chemical Industries, Ltd.

(8) Curing agent: “4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30”
-Product name: “Rikacid MH-700G” manufactured by Shin Nippon Rika Co., Ltd.

(9) Curing accelerator: Amine-based compound-Product name: "U-CAT 18X" manufactured by Sun Apro Co., Ltd.
(10) Silicone resin: “SCR-1012 (liquid A and liquid B)” manufactured by Shin-Etsu Chemical Co., Ltd.

[Example 1]
A resin composition was prepared by the following steps.
(1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer.
(2) According to the composition ratio shown in Table 1 below, the Bis-A epoxy resin, the alkoxysilane compound, and THF are placed in a flask containing a stirrer and mixed and stirred in an atmosphere at 25 ° C. Water and a hydrolysis condensation catalyst were added and mixed and stirred.
(3) Subsequently, a cooling tube was set in the flask, and the flask was quickly immersed in an oil bath at 80 ° C. to start stirring, and reacted for 25 hours while refluxing (refluxing step).
(4) After completion of the reaction, after cooling to 25 ° C., the cooling tube was removed from the flask, and after completion of the reflux step, a sample solution (intermediate) was collected.
(5) After completion of the reflux step, Si-NMR of the sample solution was measured, and the condensation rate K1 of the intermediate was determined according to the above formula (10). Intermediate condensation ratio K1 (%) = 80.1% ≧ 78%.
(6) The solution after completion of the refluxing process was distilled off at 400 Pa and 50 ° C. for 1 hour using an evaporator, and then further subjected to a dehydration condensation reaction while being distilled off at 80 ° C. for 10 hours (dehydration condensation). Process).
(7) After completion of the dehydration condensation reaction, the mixture was cooled to 25 ° C. to obtain a resin composition.
(8) The above-mentioned mixing indices α1 to ε1 of this resin composition are shown in Table 3 below.
(9) Furthermore, according to the above-mentioned method, the epoxy equivalent (WPE), the starting viscosity, and the storage viscosity of the resin composition obtained in the above (6) were measured. Furthermore, the storage stability index θ1 was obtained and shown in Table 3.
The resin composition of Example 1 had an epoxy equivalent (WPE) of 220 g / eq, and showed an appropriate value. In addition, the starting viscosity = 12.7 Pa · s <1000 Pa · s and the storage viscosity = 32.5 Pa · s <1000 Pa · s, both were fluid liquids. Further, it was found that the storage stability index θ1 = 2.6 ≦ 4, the resin composition having excellent fluidity and improved storage stability.
Next, using the above resin composition, a cured product was produced and evaluated by the following procedure.
(10) In an atmosphere at 25 ° C., the above-described resin composition, curing agent and curing accelerator were mixed and stirred according to the composition ratio shown in Table 2 below, and deaerated under vacuum to obtain a cured product solution.
(11) A 3 mm thick, U-shaped silicon rubber is sandwiched between two stainless steel plates coated with a release agent, and the cured product produced by this molding jig is about 50 mm × about 20 mm × thickness 3 mm. Thus, a molding jig was produced.
(12) The cured product solution was poured into the molding jig and the 10 thermal shock test substrates, and the silicon chips were placed on each substrate one by one.
(13) The molding jig and the thermal shock test substrate were placed in an oven, and cured at 120 ° C. for 1 hour and further at 150 ° C. for 1 hour to produce a cured product.
(14) After the oven internal temperature dropped to 30 ° C. or lower, the cured product was taken out, and a light resistance test sample and a thermal shock test sample were prepared according to the method described above.
(15) Table 3 below shows the results of the light resistance test and the thermal shock test performed by the above-described method using the sample. This cured product had YI = 11.9 ≦ 13, which is an index of a light resistance test, and was judged to have practically sufficient light resistance. Furthermore, the number of times of the thermal shock test was 300 times ≧ 100 times, and it was judged that the thermal thermal shock resistance was practically sufficient.
From the above results, the resin composition of Example 1 has good fluidity and excellent storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance. As a comprehensive judgment, it was judged that it was acceptable.

[Example 2]
By the same method as in Example 1 described above, a resin composition and a cured product thereof were prepared according to Table 1 and Table 2 below.
About this resin composition and its hardened | cured material, it evaluated by the method similar to Example 1 mentioned above. The evaluation results, the mixing indices α2 to ε2, and the storage stability index θ2 are shown in Table 3 below.
Intermediate condensation ratio K2 (%) = 78.2% ≧ 78%.
As shown in Table 3 below, the resin composition of Example 2 was epoxy equivalent (WPE) = 233 g / eq, and showed an appropriate value.
In addition, the starting viscosity = 15.9 Pa · s <1000 Pa · s and the storage viscosity = 53.8 Pa · s <1000 Pa · s, which were good fluidity.
It was also found that the resin composition had a storage stability index θ2 = 3.4 ≦ 4, excellent fluidity, and improved storage stability.
Moreover, it was judged that YI = 8.1 ≦ 13, which is an index of the light resistance test of the cured product, and that the light resistance was practically sufficient.
The number of times of the thermal shock test was 200 times ≧ 100 times, and it was judged that the thermal thermal shock resistance was practically sufficient.
From the above results, the resin composition of Example 2 has excellent fluidity and improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance. Since it has property, it was judged that it was a pass as comprehensive judgment.

Example 3
By the same method as in Example 1 described above, a resin composition and a cured product thereof were prepared according to Table 1 and Table 2 below.
About this resin composition and its hardened | cured material, it evaluated by the method similar to Example 1 mentioned above. Table 3 shows the evaluation results, the mixing indices α3 to ε3, and the storage stability index θ3.
Intermediate condensation rate K3 (%) = 85.3% ≧ 78%.
As shown in Table 3 below, the resin composition of Example 3 was epoxy equivalent (WPE) = 242 g / eq, and showed an appropriate value.
The onset viscosity was 14.3 Pa · s <1000 Pa · s and the storage viscosity was 41.0 Pa · s <1000 Pa · s, both of which were fluid liquids. Further, it was found that the resin composition had a storage stability index θ3 = 2.9 ≦ 4, excellent fluidity, and improved storage stability.
YI = 8.9 ≦ 13, which is an index of the light resistance test of this cured product, and it was judged that the light resistance was practically sufficient.
The number of times of the thermal shock test was 200 times ≧ 100, and it was judged that the thermal thermal shock resistance was practically sufficient.
From the above results, the resin composition of Example 3 has excellent fluidity and improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and cold thermal shock resistance. Since it has property, it was judged that it was a pass as comprehensive judgment.

Example 4
By the same method as in Example 1 described above, a resin composition and a cured product thereof were prepared according to Table 1 and Table 2 below.
About this resin composition and its hardened | cured material, it evaluated by the method similar to Example 1 mentioned above. Table 3 shows the evaluation results, the mixing indices α4 to ε4, and the storage stability index θ4.
Intermediate condensation rate K4 (%) = 87.4% ≧ 78%.
As shown in Table 3 below, the resin composition of Example 4 was epoxy equivalent (WPE) = 238 g / eq, and showed an appropriate value.
In addition, the starting viscosity = 15.6 Pa · s <1000 Pa · s and the storage viscosity = 24.9 Pa · s <1000 Pa · s, both were fluid liquids. Further, it was found that the storage stability index θ4 = 1.6 ≦ 4, the resin composition having excellent fluidity and improved storage stability.
YI = 8.8 ≦ 13, which is an index of the light resistance test of this cured product, and it was judged that the light resistance was practically sufficient.
The number of times of the thermal shock test was 100 times ≧ 100 times, and it was judged to have practically sufficient cold thermal shock resistance.
From the above results, the resin composition of Example 4 has excellent fluidity and improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and cold thermal shock resistance. Since it has property, it was judged that it was a pass as comprehensive judgment.

Example 5
In the same manner as in Example 1 described above, a resin composition and a cured product thereof were prepared according to Table 1 and Table 2 below.
About this resin composition and its hardened | cured material, it evaluated by the method similar to Example 1 mentioned above. The evaluation results, mixing indices α5 to ε5, and storage stability index θ5 are shown in Table 3 below.
Intermediate condensation ratio K5 (%) = 82.6% ≧ 78%.
As shown in Table 3 below, the resin composition of Example 5 was epoxy equivalent (WPE) = 245 g / eq, and showed an appropriate value.
In addition, the starting viscosity = 17.3 Pa · s <1000 Pa · s and the storage viscosity = 50.2 Pa · s <1000 Pa · s, both were fluid liquids. Further, it was found that the storage stability index θ5 = 2.9 ≦ 4, the resin composition having excellent fluidity and improved storage stability.
YI = 8.2 ≦ 13, which is an index of the light resistance test of this cured product, and it was judged that the light resistance was practically sufficient.
The number of times of the thermal shock test was 100 times ≧ 100 times, and it was judged to have practically sufficient cold thermal shock resistance.
From the above results, the resin composition of Example 5 has excellent fluidity and improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance. Since it has property, it was judged that it was a pass as comprehensive judgment.

Example 6
In the same manner as in Example 1 described above, a resin composition and a cured product thereof were prepared according to Table 1 and Table 2 below.
About this resin composition and its hardened | cured material, it evaluated by the method similar to Example 1 mentioned above. The evaluation results, mixing indices α6 to ε6, and storage stability index θ6 are shown in Table 3 below.
Intermediate condensation ratio K6 (%) = 82.8% ≧ 78%.
As shown in Table 3 below, the resin composition of Example 6 was epoxy equivalent (WPE) = 253 g / eq, and showed an appropriate value.
Further, the starting viscosity = 24.3 Pa · s <1000 Pa · s and the storage viscosity = 86.3 Pa · s <1000 Pa · s, both were fluid liquids. Further, it was found that the storage stability index θ6 = 3.6 ≦ 4, the resin composition was excellent in fluidity and improved in storage stability.
YI = 9.7 ≦ 13, which is an index of the light resistance test of this cured product, and it was judged that the light resistance was practically sufficient. Furthermore, the number of times of the thermal shock test was 200 times ≧ 200 times, and it was judged that the thermal thermal shock resistance was practically sufficient.
From the above results, the resin composition of Example 6 has excellent fluidity and improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and cold thermal shock resistance. Since it has property, it was judged that it was a pass as comprehensive judgment.

Example 7
In the same manner as in Example 1 described above, a resin composition and a cured product thereof were prepared according to Table 1 and Table 2 below.
About this resin composition and its hardened | cured material, it evaluated by the method similar to Example 1 mentioned above. The evaluation results, mixing indices α7 to ε7, and storage stability index θ7 are shown in Table 3 below.
Intermediate condensation rate K7 (%) = 83.5% ≧ 78%.
As shown in Table 3 below, the resin composition of Example 7 was epoxy equivalent (WPE) = 210 g / eq, and showed an appropriate value.
In addition, the starting viscosity = 12.8 Pa · s <1000 Pa · s and the storage viscosity = 39.8 Pa · s <1000 Pa · s, both were fluid liquids. Further, it was found that the storage stability index θ7 = 3.1 ≦ 4, the resin composition was excellent in fluidity and storage stability was improved.
YI = 7.5 ≦ 13, which is an index of the light resistance test of the cured product, and it was determined that the cured product has sufficient light resistance. Furthermore, the number of times of the thermal shock test was 300 times ≧ 100 times, and it was judged that the thermal thermal shock resistance was practically sufficient.
From the above results, the resin composition of Example 7 has excellent fluidity and improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance. Since it has property, it was judged that it was a pass as comprehensive judgment.

Example 8
In the same manner as in Example 1 described above, a resin composition and a cured product thereof were prepared according to Table 1 and Table 2 below.
Table 3 below shows the evaluation results, the mixing indexes α8 to ε8, and the storage stability index θ8, in which the resin composition and its cured product were evaluated by the same method as in Example 1 described above.
Intermediate condensation rate K8 (%) = 84.2% ≧ 78%.
As shown in Table 3 below, the resin composition of Example 8 had an epoxy equivalent (WPE) of 233 g / eq, and showed an appropriate value.
In addition, the starting viscosity = 13.2 Pa · s <1000 Pa · s and the storage viscosity = 46.8 Pa · s <1000 Pa · s, both were fluid liquids. Further, it was found that the storage stability index θ8 = 3.5 ≦ 4, the resin composition having excellent fluidity and improved storage stability.
It was judged that YI = 7.3 ≦ 13, which is an index of the light resistance test of the cured product, and had light resistance. Furthermore, the number of times of the thermal shock test was 100 times ≧ 100 times, and it was judged that the thermal thermal shock resistance was provided.
From the above results, the resin composition of Example 8 has excellent fluidity and improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance. Since it has property, it was judged that it was a pass as comprehensive judgment.

[Comparative Example 1]
The (3) reflux step shown in Example 1 was changed to 7 hours. Other conditions were the same as in Example 1, and a resin composition was prepared according to Table 1 and evaluated by the same method as in Example 1.
The evaluation results, mixing indices α9 to ε9, and storage stability index θ9 are shown in Table 3 below.
Intermediate condensation rate K9 (%) = 64.8% <78%.
As shown in Table 3 below, the resin composition of Comparative Example 1 was epoxy equivalent (WPE) = 231 g / eq, and showed an appropriate value. The onset viscosity was 11.8 Pa · s <1000 Pa · s. However, storage viscosity> 1000 Pa · s, no fluidity, storage stability index θ9> 84 and storage stability were poor.
As shown in Table 3, the light resistance and the thermal shock resistance of the cured product using the resin composition of Comparative Example 1 were good, but the storage stability of the resin composition was poor, and the comprehensive judgment was Judgment was rejected.

[Comparative Example 2]
The curing treatment temperature of (13) shown in Example 1 was changed to 110 ° C. for 4 hours and further to 150 ° C. for 1 hour. Other conditions were the same as in Example 1, and a resin composition and a cured product were prepared according to Table 1 and Table 2 below, and evaluated in the same manner as in Example 1.
The evaluation results, mixing indices α10 to ε10, and storage stability index θ8 are shown in Table 3 below.
Intermediate condensation rate K10 (%) = 71.1% <78%.
As shown in Table 3 below, the resin composition of Comparative Example 2 was epoxy equivalent (WPE) = 200 g / eq, and showed an appropriate value.
The onset viscosity was 11.7 Pa · s <1000 Pa · s. However, storage viscosity> 1000 Pa · s, indicating no fluidity, storage stability index θ10> 85, and storage stability was poor.
As shown in Table 3, the light resistance and the thermal shock resistance of the cured product using the resin composition of Comparative Example 2 were good, but the storage stability of the resin composition was poor, and the comprehensive judgment was not good. Judged to pass.

[Comparative Example 3]
A cured product was produced according to Table 2 by the same method as in Example 1 described above. This cured product was evaluated by the same method as in Example 1.
The evaluation results are shown in Table 3 below.
It was determined that YI = 16.9> 13, which is an index of the light resistance test of the cured product, and that there was no practical light resistance. Further, the number of times of the thermal shock test was 500 times or more and ≧ 100 times, and it was judged that the thermal shock resistance was practically sufficient.
From the above results, the cured product of Comparative Example 3 was judged to be rejected as a comprehensive judgment because it had cold-heat shock resistance but lacked light resistance.

[Comparative Example 4]
According to Table 2 below, a silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., “SCR-1012 (A liquid and B liquid)”) prepared by mixing and stirring A liquid and B liquid at a mass ratio of 1: 1. A cured product solution was prepared in the same manner as in Example 1.
In the same manner as in Example 1, this curing solution was poured into the molding jig and the 10 thermal shock test substrates described above, and the cured product solution was poured into each substrate, and a silicon chip was placed on each substrate. I put them one by one.
The molding jig and the thermal shock test substrate were placed in an oven and subjected to curing treatment at 70 ° C. for 1 hour and further at 150 ° C. for 5 hours to prepare a cured product.
This cured product was evaluated by the same method as in Example 1.
The evaluation results are shown in Table 3 below.
YI = 2.0 ≦ 13, which is an index of the light resistance test of the cured product, and it was judged that the light resistance was practically sufficient. However, the number of times of the thermal shock test is 0 <100 times, and it has been found that there is no practically sufficient thermal shock resistance.
From the above results, the cured product of Comparative Example 4 was judged to be unacceptable as a comprehensive judgment because it had light resistance but lacked thermal shock resistance.

[Comparative Example 5]
The dehydration condensation process was performed for 25 hours.
Other conditions were the same as in Comparative Example 1, and a resin composition was prepared according to Table 1 and evaluated by the same method as in Example 1.
The evaluation results, mixing indices α11 to ε11, and storage stability index θ11 are shown in Table 3 below.
Intermediate condensation rate K11 (%) = 64.8% <78%.
As shown in Table 3 below, the resin composition of Comparative Example 5 was epoxy equivalent (WPE) = 233 g / eq, and showed an appropriate value. The onset viscosity was 15.2 Pa · s <1000 Pa · s. However, storage viscosity> 1000 Pa · s, fluidity was not exhibited, storage stability index θ11> 66 and storage stability were poor, and the comprehensive judgment was judged as unacceptable.
From the above, even if the time for performing the dehydration condensation process is extended, the storage stability of the resin composition does not reach the pass line, and the characteristics of the resin composition are the condensation rate of the intermediate in the reflux process (chemical structure) It turned out to depend greatly on.

[Comparative Example 6]
The temperature of the oil bath in the reflux process was changed to 60 ° C.
Other conditions were the same as in Example 4, and a resin composition was prepared according to Table 1 and evaluated by the same method as in Example 1.
The evaluation results, mixing indices α12 to ε12, and storage stability index θ12 are shown in Table 3 below.
Intermediate condensation rate K12 (%) = 63.6% <78%.
As shown in Table 3 below, the resin composition of Comparative Example 6 had an epoxy equivalent (WPE) of 238 g / eq, and showed an appropriate value. The onset viscosity was 16.4 Pa · s <1000 Pa · s. However, storage viscosity> 1000 Pa · s, fluidity was not exhibited, storage stability index θ12> 61 and storage stability was poor, and the overall judgment was judged as unacceptable.
From the above, even when the composition was the same as that of the resin composition of Example 4, the storage stability of the resin composition did not reach the pass line. From this result, it was found that the characteristics of the resin composition largely depend on the condensation rate (chemical structure) of the intermediate in the refluxing process.

  As shown in Tables 1 to 3, the epoxy resin and the specific alkoxysilane compound are mixed at a specific ratio, the condensation rate of the intermediate in the refluxing step of the cohydrolysis condensation is specified, and then the dehydration condensation is performed. The resin compositions of Examples 1 to 8 produced by performing have excellent fluidity and storage stability, and the cured products of these resin compositions are all excellent in light resistance and cold heat resistance. It was found to have impact properties.

  The resin composition and cured product of the present embodiment are, for example, electronic materials (insulators, AC transformers, switchgear and other castings and circuit units, various component packages, ICs, LEDs, semiconductors and other sealing materials , Generators, motors and other rotating machine coils, winding impregnation, printed wiring boards, insulation boards, medium-sized insulators, coils, connectors, terminals, various cases, electrical parts, etc.) Have

Claims (7)

(A) an epoxy resin;
An alkoxysilane compound represented by the following formula (1);
Having a step of cohydrolyzing and condensing,
In the co-hydrolytic condensation step, a method for producing a resin composition in which an intermediate produced in a reflux step without dehydration having a condensation rate of 78% or more is dehydrated and condensed.

(In the formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group.
² may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
And the mixture index α of (B) and (C) represented by the following formula (2) is 0.001 to 0.001.
19.
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)) The method for producing a resin composition according to claim 1, wherein the epoxy resin (A) has an epoxy equivalent (WPE) of 100 to 600 g / eq and a viscosity at 25 ° C of 1000 Pa · s or less. The (A) epoxy resin is
The method for producing a resin composition according to claim 1 or 2, which is a glycidyl etherified product of a polyphenol compound and is a polyfunctional epoxy resin. As the alkoxysilane compound,
(D): The method for producing a resin composition according to any one of claims 1 to 3, further comprising at least one alkoxysilane compound in which n = 0 in the formula (1). A mixing index β of the alkoxysilane compound represented by the following formula (3) is 0.01 to 1.
The method for producing a resin composition according to claim 1, wherein the resin composition is 4.
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
here,
β ⁿ² : content of alkoxysilane compound in which n = 2 in the formula (1) (mo
l%)
β ⁿ⁰ : Content of alkoxysilane compound in which n = 0 in the formula (1) (mo
l%)
β ⁿ¹ : Content of alkoxysilane compound in which n = 1 in the formula (1) (mo
l%)
And
0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1. Represented by the following formula (4),
The mixing index γ of the (A) epoxy resin and the alkoxysilane compound is 0.02 to
The method for producing a resin composition according to claim 1, wherein the resin composition is 15.
Mixing index γ = (γa) / (γs) (4)
In the formula (4),
γa: mass of epoxy resin (g),
γs: Mass (g) of alkoxysilane compound in which n = 0 to 2 in the general formula (1)
It is. The method for producing a resin composition according to any one of claims 1 to 6, wherein the cohydrolysis condensation is performed in the presence of (E) an alkali organic metal which is a hydrolysis condensation catalyst.